U.S. patent application number 13/525804 was filed with the patent office on 2012-10-11 for process for producing a rubber anti-aging agent, a vulcanization accelerator or modified natural rubber by means of microorganism.
Invention is credited to Keitaro FUJIKURA.
Application Number | 20120259048 13/525804 |
Document ID | / |
Family ID | 41317982 |
Filed Date | 2012-10-11 |
United States Patent
Application |
20120259048 |
Kind Code |
A1 |
FUJIKURA; Keitaro |
October 11, 2012 |
PROCESS FOR PRODUCING A RUBBER ANTI-AGING AGENT, A VULCANIZATION
ACCELERATOR OR MODIFIED NATURAL RUBBER BY MEANS OF
MICROORGANISM
Abstract
An object of the present invention is to provide processes for
producing a rubber anti-aging agent, a vulcanization accelerator
and a modified natural rubber, by converting glucose into benzoic
acid or a benzoic acid derivative by a microorganism or extracting
benzoic acid or a benzoic acid derivative from a plant, converting
the obtained benzoic acid or benzoic acid derivative into aniline
or an aniline derivative and then making the rubber anti-aging
agent, vulcanization accelerator or modified natural rubber with
the aniline or aniline derivative.
Inventors: |
FUJIKURA; Keitaro;
(Kobe-shi, JP) |
Family ID: |
41317982 |
Appl. No.: |
13/525804 |
Filed: |
June 18, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
12469939 |
May 21, 2009 |
8222011 |
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13525804 |
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Current U.S.
Class: |
524/186 ;
435/128; 564/394 |
Current CPC
Class: |
C07C 209/56 20130101;
C07C 209/56 20130101; C07C 211/46 20130101; C12P 7/40 20130101 |
Class at
Publication: |
524/186 ;
435/128; 564/394 |
International
Class: |
C08K 5/18 20060101
C08K005/18; C07C 209/00 20060101 C07C209/00; C08L 7/00 20060101
C08L007/00; C12P 13/00 20060101 C12P013/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 10, 2008 |
JP |
2008-151413 |
Apr 10, 2009 |
JP |
2009-096016 |
Claims
1. A process for producing an antiaging agent, which process
comprises: converting glucose into benzoic acid or a benzoic acid
derivative by a microorganism other than Streptomyces maritimus and
Streptomyces coelicolor, or extracting benzoic acid or a benzoic
acid derivative from a plant; and converting the obtained benzoic
acid or benzoic acid derivative into aniline or an aniline
derivative.
2. A process for producing a vulcanization accelerator, which
process comprises: converting glucose into benzoic acid or a
benzoic acid derivative by a microorganism other than Streptomyces
maritimus and Streptomyces coelicolor, or extracting benzoic acid
or a benzoic acid derivative from a plant; and converting the
benzoic acid or benzoic acid derivative into aniline or an aniline
derivative.
3. A process for producing a modified natural rubber, which process
comprises: converting glucose into benzoic acid or a benzoic acid
derivative by a microorganism other than Streptomyces maritimus and
Streptomyces coelicolor, or extracting benzoic acid or a benzoic
acid derivative from a plant; converting the benzoic acid or
benzoic acid derivative into aniline or an aniline derivative; and
modifying a natural rubber by the aniline or aniline derivative.
Description
CROSS REFERENCE
[0001] The present application is a 37 C.F.R. .sctn.1.53 (b)
divisional of, and claims priority to, U.S. application Ser. No.
12/469, 939, filed May 21, 2009. Priority is also claimed to
Japanese Application No. 2008-151413 filed on Jun. 10, 2008 and
Japanese Application No. 2009-096016 filed on Apr. 10, 2009. The
entire contents of each of these applications is hereby
incorporated by reference.
TECHNICAL FIELD
[0002] The present invention relates to a process for producing an
antiaging agent, a vulcanization accelerator or a modified natural
rubber by means of a microorganism or a plant. More particularly,
the present invention relates to a process for producing an
antiaging agent, a vulcanization accelerator or a modified natural
rubber by using benzoic acid or a benzoic acid derivative produced
by a microorganism or extracted from a plant.
BACKGROUND ART
[0003] At present, antiaging agents used for a rubber, thiazole
vulcanization accelerators and sulfenamide vulcanization
accelerators are synthesized from aniline which is produced from
petroleum as a raw material. Assuming a rise in oil prices and
exhaustion of oil in the future, a production process which does
not use oil is desired. Further, processes of production of
antiaging agents and vulcanization accelerators cause global
warming since industrial production of aniline from petroleum
resources emit a large amount of heat and carbon dioxide.
Therefore, based on an idea of utilizing natural resources, a
method is known wherein a vulcanization accelerator is synthesized
by the use of a naturally-derived long-chain amine, as a material,
which is obtained by reductive amination of a saturated or
unsaturated fatty acid which is obtained by hydrolysis of a natural
fat and oil (Patent Document 1).
[0004] However, acrylonitrile, mercaptobenzothiazoles and
dibenzothiazolyl disulfide are used in the process of producing
vulcanization accelerators. There is no description that these
materials are produced from natural resources.
[0005] Further, a production process is known wherein a modified
natural rubber is produced by a graft polymerization or an addition
of a compound containing a polar group under mechanical shear
stress to a natural rubber raw material (Patent Document 2) .
However, it is not assumed that a naturally-derived material is
used as a compound containing a polar group.
[0006] Patent Document 1: JP-A-2005-139239
[0007] Patent Document 2: JP-A-2006-152171
SUMMARY OF THE INVENTION
[0008] It is an object of the present invention to provide
processes for producing an antiaging agent, a vulcanization
accelerator and a modified natural rubber, which are
environmentally friendly and capable of making provision against a
decrease of petroleum resources in the future.
[0009] The present invention relates to a process for producing an
antiaging agent, which comprises: converting glucose into benzoic
acid or a benzoic acid derivative by a microorganism or extracting
benzoic acid or a benzoic acid derivative from a plant; and
converting the obtained benzoic acid or benzoic acid derivative
into aniline or an aniline derivative.
[0010] The present invention also relates to a process for
producing a vulcanization accelerator, which comprises: converting
glucose into benzoic acid or a benzoic acid derivative by a
microorganism or extracting benzoic acid or a benzoic acid
derivative from a plant; and converting the benzoic acid or benzoic
acid derivative into aniline or an aniline derivative.
[0011] The present invention also relates to a process for
producing a modified natural rubber, which comprises: converting
glucose into benzoic acid or a benzoic acid derivative by a
microorganism or extracting benzoic acid or a benzoic acid
derivative from a plant; converting the benzoic acid or benzoic
acid derivative into aniline or an aniline derivative; and
modifying a natural rubber by the aniline or aniline
derivative.
DETAILED DESCRIPTION OF THE INVENTION
[0012] In the following, the present invention is described in
detail.
[0013] In the present invention, glucose is used as carbon neutral
resources and is converted into benzoic acid or a benzoic acid
derivative by a microorganism. Alternatively, benzoic acid or a
benzoic acid derivative is extracted from a plant; thereafter, the
obtained benzoic acid or benzoic acid derivative is converted into
aniline or an aniline derivative. An antiaging agent, a
vulcanization accelerator or a modified natural rubber is produced
from the thus obtained aniline or aniline derivative.
[0014] The production of the aniline or aniline derivative from a
plant or a microorganism requires a nitrogen source; however, since
benzoic acid or a benzoic acid derivative is produced in the
present invention, it can be produced without using a nitrogen
source.
[0015] In the case where glucose is converted into benzoic acid or
a benzoic acid derivative by a microorganism, the glucose used is
obtained from plants which take in carbon dioxide in the
atmosphere. The examples thereof may include waste wood, paddy
straw, weed and non-edible part of food crop (stem, root and xylem)
. Glucose can be obtained by adding an acid to the materials and
hydrolyzing them or carrying out a hot-compressed water treatment.
In this process, since glucose is converted into the benzoic acid
or benzoic acid derivative, it is not necessary to add a nitrogen
source.
[0016] Here, examples of the benzoic acid derivative may include a
compound in which a substituent group, such as a hydroxyl group and
a carboxy group, is replaced on the benzene ring of benzoic acid.
Examples of a preferable benzoic acid derivative may include
salicylic acid, and the like.
[0017] Examples of the microorganism used when converting glucose
into benzoic acid or a benzoic acid derivative by a microorganism
may include Streptomyces maritimus (EMBL AAF81726), Streptomyces
coelicolor (ATCC10147), and the like.
[0018] Conversion of glucose into benzoic acid or a benzoic acid
derivative can be carried out in water or a solvent which is a
mixture of water and an organic solvent. Examples of the organic
solvent may include methanol, ethanol, dimethyl sulfoxide, diethyl
ether, tetrahydrofuran and acetone.
[0019] Temperature for conversion is preferably 20.degree. C. to
42.degree. C. If the temperature is below 20.degree. C., activity
of the microorganism may be depressed. If the temperature is above
42.degree. C., the microorganism tends to be killed. Therefore, in
both cases yield decreases. It is more preferable that the lower
limit is 25.degree. C. and the upper limit is 30.degree. C.
[0020] It is preferable that pH is between 4 and 9 during the
reaction. If pH is not within the above range, production
efficiency of benzoic acid may drop extremely.
[0021] Cultivation time may be 3 to 9 days, preferably 4 to 7
days.
[0022] The plants used upon extracting benzoic acid or a benzoic
acid derivative take in carbon dioxide in the atmosphere, and
examples thereof include Styrax benzoin (Order: Ericales, Family:
Styracaceae), Hypericum androsaemum (Order: Theales, Family:
Guttiferae), and the like. The plants can be obtained by refining
the resin "benzoin", which is obtainable by solidifying the sap
obtained by scratching the trees of the Family Styracaceae.
[0023] The benzoic acid or benzoic acid derivative obtained by the
use of a microorganism or a plant can synthesize aniline through
the synthetic pathway without petroleum resources. Examples of the
synthetic pathway may include the Hoffmann rearrangement reaction,
the Curtius rearrangement reaction, and the like. In the Hoffmann
rearrangement reaction, aniline can be synthesized through the
following synthetic pathway.
##STR00001##
[0024] Examples of the aniline derivative may include compounds
which have a substituent such as hydroxyl group or carboxyl group
on the benzene ring of aniline. Preferable aniline derivatives
include 3-carboxy-6-hydroxyaniline.
[0025] Examples of the antiaging agent may include
N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine as
p-phenylenediamine antiaging agent, and polymer of
2,2,4-trymethyl-1,2-dihydroquinoline as quinoline antiaging
agent.
[0026] For example,
N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine can be produced
from aniline by the following synthesis approach. Here, methyl
isobutyl ketone which is added to the amine, an intermediate, can
be synthesized by dry distillation of calcium acetate or aldol
condensation of acetone which is obtained by acetone-buthanol
fermentation. These methods make it possible to produce the
compound without petroleum resources.
##STR00002##
[0027] Polymer of 2,2,4-trimethyl-1,2-dihydroquinoline can be
produced from aniline by continually supplying acetone as needed at
140.degree. C. in the presence of an acidic catalyst. The method
makes it possible to produce the compound without petroleum
resources.
[0028] Examples of the vulcanization accelerator may include
2-mercaptobenzothiazole and dibenzothiazyl disulfide as thiazole
vulcanization accelerators, and N-cyclohexyl-2-benzothiazyl
sulfenamide, N,N-dicyclohexyl-2-benzothiazyl sulfenamide, and
N-tert-butyl-2-benzothiazyl sulfenamide as sulfenamide
vulcanization accelerators.
[0029] 2-Mercaptobenzothiazole can be produced from aniline by the
following synthesis approach. Here, carbon disulfide can be
generated and separated, for example, by reacting about 0.4% of
mustard oil, which is contained in leaf mustard, with hydrogen
sulfide. The method makes it possible to produce the vulcanization
accelerator without petroleum resources. Dibenzothiazyl disulfide
is synthesized by oxidizing thus produced
2-mercaptobenzothiazole.
##STR00003##
[0030] As a natural rubber, deproteinized natural rubber can be
used as well as normal natural rubber. Modified natural rubber can
be produced by graft polymerization of aniline and natural rubber
under electron beam irradiation, mechanical shear stress and the
like.
[0031] The antiaging agents, vulcanization accelerators or modified
natural rubbers, which are obtained by the production process of
the present invention, can be used as materials for normal rubber
products, and are especially useful as rubber compositions used for
tires.
[0032] The rubber composition can be produced by mixing inorganic
fillers such as clay, aluminum hydroxide and calcium carbonate, and
compounding agents which are used in ordinary rubber industry such
as process oil, softeners, antiaging agents, vulcanization agents
and vulcanization aids as needed as well as rubber components,
silica, silane coupling agents, carbon black and vulcanization
accelerators.
[0033] The rubber composition is produced by kneading rubber
components and necessary compounding agents with a rubber kneading
machine such as a bunbury mixer or an open roll, kneading various
additives if necessary, extruding thus obtained unvulcanized rubber
composition into a form of respective tire parts, forming an
unvulcanized tire on a tire molding machine, and hot pressing the
unvulcanized tire in a vulcanizer.
[0034] According to the present invention, an antiaging agent, a
vulcanization accelerator or a modified natural rubber is produced
from benzoic acid or a benzoic acid derivative obtained by the use
of a microorganism or a plant. The process is environmentally
friendly and makes it possible to make provision against a decrease
of petroleum resources in the future.
BEST MODES FOR CARRYING OUT THE INVENTION
[0035] The following examples illustrate the present invention
specifically. They, however, do not limit the scope of the present
invention.
EXAMPLES
[0036] (Example of production of benzoic acid using a
microorganism)
[0037] As a starting material, glucose was controlled to have a
concentration of 5%. Al culture medium was heat-treated at
120.degree. C. for 20 minutes and cooled to room temperature.
Streptomyces Maritimes was cultured at pH 7.5, 28.degree. C., 170
rpm, over 4 to 5 days under aerobic condition in the culture
medium. Diethyl ether was then added to the culture medium and
extraction was carried out twice. A crude extract was concentrated
by an evaporator and purified by flash chromatography using a
column filled with silica gel 60. Benzoic acid was identified by
NMR and IR.
(Example of production of benzoic acid from a plant)
[0038] An amount of 25 g of ground Siam benzoin resin was dispersed
in 500 ml of a solution (pH of 3) prepared by adding hydrochloric
acid to water and was extracted five times by using 20 v/v% of
diethylether in a separatory funnel. The combined ether layer was
evaporated to remove solvents until the volume thereof reached 5
ml. Benzoic acid with a concentration of 5 g/l was detected by HPLC
analysis.
(Example of production of aniline from benzoic acid)
[0039] An amount of 500 g of benzoic acid was dissolved in 2000 ml
of acetone, and 400 g of thionyl chloride was added dropwise over 3
hours. Thereafter, the mixture was stirred at a room temperature
overnight under reflux. The solvent and unreacted thionyl chloride
were removed to give 231 g of benzoyl chloride. Subsequently, the
thus obtained benzoyl chloride was dissolved in 2000 ml of acetone
and decompressed to 25 mmHg with an aspirator in a cooled state at
5.degree. C. or less, and thereafter ammonia gas was purged
therein. The reaction was stopped when the reaction system returned
to normal pressure, and the reaction mixture was filtered under
reduced pressure to obtain 169 g of ammonium benzoate. After the
ammonium benzoate was washed with 1000 ml of water and then
dissolved in 1N aqueous ice-cooled sodium hydroxide solution,
bromine was added thereto. Thereby, the hydrolysis and
decarboxylation was caused through the Hoffmann rearrangement to
give the target 10.9 g of aniline.
(Example of production of antiaging agent from aniline)
[0040] To a flask equipped with an acetone introduction apparatus,
a distillation apparatus, a thermometer and an agitator were added
190 g (2.0 mol) of aniline which was obtained through the
production method and hydrochloric acid (0.20 mol) as an acidic
catalyst, and then heated to 140.degree. C. The reaction system was
kept at 140.degree. C., and 580 g (10 mol) of acetone was
continuously supplied to the reaction system for 6 hours. Distilled
unreacted acetone and aniline were returned to the reaction system
occasionally. As a result, 180.7 g (yield: about 30%) of polymer of
2,2,4-trimethyl-1,2-dihydroquinoline was obtained. Its degree of
polymerization is 2 to 4. Unreacted aniline and monomer of
2,2,4-trimethyl-1,2-dihydroquinoline were recovered by distillation
under reduced pressure. Unreacted aniline distilled at 140.degree.
C., and the monomer distilled after the temperature was raised to
190.degree. C. Yield of the monomer was 19.1 g (6.9%).
(Method for preparing carbon disulfide from sources other than
petroleum resources)
[0041] Carbon disulfide was obtained by reacting about 0.4% of
mustard oil, which is contained in leaf mustard, with hydrogen
sulfide or by heating charcoal and sulfur at 900.degree. C.
(Method for producing vulcanization accelerator from aniline)
[0042] An amount of 93 g (1.0 mol) of aniline obtained in the
above-mentioned example of production, 80 g (1.1 mol) of carbon
disulfide obtained by the above-mentioned preparation method, and
16 g (1.0 mol) of sulfur were charged to a 300 ml compression
reactor, reacted at 250.degree. C. and 10 MPa for two hours, and
thereafter cooled down to 180.degree. C. to prepare crude
2-mercaptobenzothiazole. The yield was 130 g (87%).
(Example of producing graft copolymer of natural rubber and
aniline)
[0043] Charged to a 4-necked flask equipped with a stirring rod, a
dropping funnel, a nitrogen introducing pipe, and a condenser was
an amount of 300 g of natural rubber latex, and then added thereto
were 250 ml of distilled water, 1.0 g of polyoxylaurylether, 5.0 g
of aniline obtained in the above-mentioned example of production,
91.6 g of methyl methacrylate under slow stirring under a nitrogen
atmosphere. Thereafter, the mixture was vigorously stirred to mix
each medicine sufficiently. Subsequently, 1.5 g of potassium
persulfate was added thereto, and reacted at 60.degree. C. for five
hours to produce a graft copolymer.
* * * * *